Cross-linked networks from multifunctional hyperbranched polymers

ABSTRACT

Hyperbranched polymers having a plurality of at least two different types of functional groups are described. Specific embodiments include hyperbranched polymers having functional groups of a first type that are substantially uniformly distributed throughout the hyperbranched polymer molecule and a second type of functional group that is substantially uniformly distributed at the terminals of the hyperbranched polymer molecule. The hyperbranched polymers having different types of functional groups are synthesized by reacting one or more monomers having functional groups that are capable of reacting during a set of polymerization conditions to form a hyperbranched polymer, wherein at least one of the monomers contains latent functional groups that are not reactive during polymerization.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a divisional of U.S. application Ser. No.09/970,366 entitled HYPERBRANCHED POLYMERS WITH LATENT FUNCTIONALITY ANDMETHODS OF MAKING SAME, filed Oct. 3, 2001, the entire disclosure ofwhich is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This invention relates to hyperbranched polymers having differenttypes of reactive functional groups and methods of preparinghyperbranched polymers having different reactive functional groups.

BACKGROUND OF THE INVENTION

[0003] Hyperbranched polymers are tree-like macromolecules that possessmore extensive chain branching than traditional branched polymerscontaining mostly primary and secondary branches attached primarily tolinear main-chain backbones, but less extensive and regular thanperfectly branched dendrimers. In other words, hyperbranched polymershave a molecular architecture that is intermediate between traditionalbranched polymers and ideally branched dendrimers.

[0004] While several different types of dendrimers containing differentreactive functional groups have been prepared by various syntheticstrategies, no such counterparts have been reported for hyperbranchedpolymers. A notable exception to this is hyperbranched macromoleculesthat result from AB_(x) polymerization and that ideally contain a singleA group in the focal point, if cyclization is suppressed. However, thissingle functional group per hyperbranched polymer molecule may not beavailable for further reaction due to such factors as steric hindranceand intramolecular cyclization, and the single functional group isnormally present at a negligible concentration such that it generallydoes not have any utility. Therefore, hyperbranched polymers having aplurality of different functional groups per molecule, and particularlytwo different functional groups that are reactive under differentconditions, are presently unknown.

SUMMARY OF THE INVENTION

[0005] This invention pertains to hyperbranched polymers having aplurality of each of at least two different types of functional groups.

[0006] In one aspect of the invention, the two different functionalgroups, are reactive under different conditions. In other words, a firsttype of functional group is reactive and a second type of functionalgroup is not reactive under a first set of conditions, and the firsttype of functional group is not reactive and the second type offunctional group is reactive under a second set of conditions. Thisallows the first type of functional group to be used for one purpose,such as for cross-linking the hyperbranched polymer molecules to form anetwork structure, and the second type of functional group for anotherpurpose, such as to form a nanoscopic domain which can act as aparticle-like reinforcing agent within the hyperbranched polymernetwork. In addition to this, the second type of functional group canalso be used for attachment of a variety of species, such as moleculesof drugs, markers, sensors, catalysts, etc.

[0007] Other aspects of the invention relate to cross-linked polymernetworks containing hyperbranched domains having a plurality of each ofat least one type of functional groups: cross-linked polymer networkscontaining a nanoscopic inorganic reinforcing agent covalently bonded tothe polymer network, hyperbranched polymers containing nanoscopicinorganic particles distributed in and covalently bonded to thehyperbranched polymer, methods of synthesizing hyperbranched polymershaving a plurality of each of at least two different types of functionalgroups, methods of forming cross-linked polymer networks fromhyperbranched polymers having a plurality of each of at least twodifferent types of functional groups, methods of preparing cross-linkedpolymer networks containing a nanoscopic reinforcing agent covalentlybonded to the polymer network, and methods of preparing hyperbranchedpolymers containing nanoscopic inorganic particles distributed in andcovalently bonded to the hyperbranched polymer.

[0008] These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009]FIG. 1 is a schematic representation of the formation of aninter-domained cross-linked network accompanied by and/or followed byintra-domain cross-linking through latent functionalities (HBP:hyperbranched polymer (network precursor); PDMS polydimethylsiloxane).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The term “hyperbranched polymer” as used in this specification,including the claims, is not intended to encompass dendrimers.Dendrimers of a given generation are monodispersed (typically having apolydispersity of less than about 1.02) highly defined globularmolecules, having a degree of branching that is 100%, or very nearly100%. They are prepared by a series of controlled stepwise growthreactions which generally involve protect-deprotect strategies andpurification procedures at the conclusion of each step. As aconsequence, synthesis of dendrimers is a tedious and expensive processthat places a practical limitation on their applicability.

[0011] As is the case with all dendritic polymers (including dendrimers,hyperbranched polymers, and the like), hyperbranched polymers arepolymers having branches upon branches. However, in contrast todendrimers, hyperbranched polymers may be prepared in a one-step,one-pot procedure. This facilitates the synthesis of large quantities ofmaterials, at high yields, and at a relatively low cost. Also, theproperties of hyperbranched polymers are different from those ofcorresponding dendrimers due to imperfect branching and rather largepolydispersities, both of which are governed mainly by the statisticalnature of the chemical reactions involved in their synthesis. Therefore,hyperbranched polymers may be viewed as intermediate between traditionalbranched polymers and dendrimers. More specifically, a hyperbranchedpolymer molecule contains a mixture of linear and branched repeatingunits, whereas an ideal dendrimer contains only branched repeatingunits. The degree of branching, which reflects the fraction of branchingsites relative to a perfectly branching system (i.e., an idealdendrimer), for a hyperbranched polymer is greater than 0 and less than1, with typical values being from about 0.25 to about 0.45. Unlike idealdendrimers which have a polydispersity of 1, hyperbranched polymers havetypical polydispersities being greater than 1.1 even at a relatively lowmolecular weight such as 1,000 Daltons, and greater than 1.5 atmolecular weights of about 10,000 or higher. These differences betweenthe polydispersities and degree of branching of hyperbranched polymersand dendrimers are indicative of the relatively higher non-ideality,randomness, and irregularity of hyperbranched polymers as compared withdendrimers, and distinguish hyperbranched polymers from dendrimers.

[0012] The hyperbranched polymers of this invention may be prepared byany applicable polymerization method, including: (a) monomolecularpolymerization of A_(x)B_(y)C_(z) monomers, wherein A and B are moietiesthat are reactive with each other but not significantly reactive withthemselves, x and y are integers having a value of at least 1 and atleast one of x or y has a value of at least 2, C is a functional groupthat is not significantly reactive with either the A or B moieties oritself during polymerization of the hyperbranched polymer and z is aninteger having a value of 1, or greater; (b) copolymerization orbi-molecular polymerization of A_(x)C_(z) and B_(y) monomers, wherein A,B and C are moieties as defined above, x and y are integers one of whichhaving a value of at least 2 and the other having a value greater than2, and z is an integer having a value of at least 1; and (c)multi-molecular polymerization reactions of two or more polyfunctionalmonomers, wherein the functionality of A or B is at least 2, while thefunctionality of at least one of A or B is higher than 2 (e.g.,A₂+A₂C_(z)+B₃). The invention also encompasses other syntheticstrategies wherein one or more monomers used in the synthesis ofhyperbranched polymers contains a latent functional group or groups thatdo not react significantly under the polymerization conditions. Forexample, two different monomers each having a latent functional group ofthe same or different type can be reacted to form a hyperbranchedpolymer in accordance with this invention (i.e., A_(x)C_(z)+B_(y)C_(w)or A_(x)C_(z)+B_(y)D_(w), wherein A, B, C, x, y, and z are as definedabove, and D is a second kind of latent functional group that does notreact significantly during the A+B polymerization and w is an integerhaving a value of at least 1). Also, a single monomer (e.g.,A_(x)B_(y)C_(z)D_(w)) having x number of A groups and y number of Bgroups that react with each other during the polymerization and z numberof C groups and w number or D groups can be polymerized to form ahyperbranched polymer containing two different types of latentfunctional groups that are not reactive during the A+B polymerizationbut are reactive under another set of conditions. In each of the aboveexamples, at least one of x and y must be an integer equal or greaterthan 2 in order to form a hyperbranched polymer. Other syntheticstrategies that may be employed may include any of the preceding systemsinvolving more than two types of reacting functional groups and/orsystems involving simultaneous polymerization reactions, such asmulti-bond opening or ring opening reactions, step-growthpolycondensations or polyadditions, and chain-growth polymerizations. Ingeneral, in order to allow synthesis and prevent premature reaction ofAB_(x), A_(x)B_(y), A_(x)B_(y)C_(z), A_(x)B_(y)C_(z)D_(w) or the likemonomers, the A and B groups should be unreactive with each other underone set of conditions, such as at normal ambient conditions, butreactive under another set of conditions, such as in the presence of aninitiator, catalyst, heating or other type of activation.

[0013] In accordance with one aspect of this invention, a hyperbranchedpolycarbosiloxanes with latent alkoxy functionalities for example may besynthesized by a hydrosilylation polymerization reaction of compoundshaving two or more vinyl, allyl or other homologous functional groupwith a dihydrido—or polyhydrido-silane or siloxane, wherein at least oneof the monomers includes at least three functional groups that arereactive during polymerization conditions and at least one of themonomers includes at least one latent alkoxy functional group that issubstantially unreactive under the polymerization conditions. U.S.patent application Ser. No. 09/753,380, filed Jan. 2, 2001, the contentsof which are incorporated by reference herein, describes synthesis ofvarious hyperbranched polycarbosilanes, polycarbosiloxanes, andpolycarbosilazenes. An example of such a reaction system may berepresented by the following equations:

[0014] *Where R may be methyl, ethyl, or other monofunctional radical,DVTMDS denotes 1,3-divinyltetramethyldisiloxane.

[0015] As illustrated above, the hyperbranched polymers of thisinvention can be a copolymer of a first monomer having two or more vinylor allyl reactive functional groups and a second monomer having three ormore hydrosilyl reactive functional groups, with at least one of themonomers having at least one latent functional group (such as OR in theprevious equations) that does not react significantly duringpolymerization of the hyperbranched polymer, and with at least one ofthe monomers having three or more reactive functional groups that doreact during the polymerization.

[0016] In accordance with a preferred aspect of the invention, thelatent functional groups that do not react significantly duringpolymerization of the hyperbranched polymer may be a hydrolyzable groupbonded to a silicon atom. Examples of hydrolyzable groups which canserve as the latent functional groups of the hyperbranched polymersinclude halogen atoms, —OR, —OCOR, anhydride and —ON═CR′R″, wherein R,R′ and R″ represent an aliphatic or aromatic hydrocarbon group.Preferred hydrolyzable groups include chloro, acetoxy, methoxy andethoxy groups.

[0017] Some specific examples of monomers having vinyl or allyl reactivefunctional groups and latent hydrolyzable groups includedivinyldichlorosilane, 1,3-divinyl-1,3-dimethyl-1,3-dichloro-disiloxane,1,3-divinyltetraethoxydisiloxane, trivinylethoxysilane, andtrivinylmethoxysilane. These monomers can be reacted with monomer havingtwo or more hydrosilyl groups and optionally including latenthydrolyzable groups to produce hyperbranched polymers in accordance withthis invention which have two different types of functional groups,including hydrolyzable groups substantially uniformly distributedthroughout the hyperbranched polymer molecule and either vinyl, allyl orhydrosilyl groups substantially uniformly distributed as terminalend-groups of the hyperbranched polymer molecules.

[0018] Examples of monomers having hydrosilyl groups that can be reactedwith the vinyl or allyl functional monomers include hydrosilylfunctional monomers without latent hydrolyzable groups, such as1,1,3,3-tetramethyldisiloxane, methyltris(dimethylsiloxy)silane,phenyltris(dimethylsiloxy)silane, methylhydrocyclosiloxanes,tetrakis(dimethylsiloxy)silane, dimethylsilane, diethylsilane,diphenylsilane, phenylmethylsilane, methylsilane, phenylsilane, etc.

[0019] Examples of monomer containing both hydrosilyl groups and latenthydrolyzable groups include dichlorosilane, dimethoxysilane, etc. Thesemonomers can be reacted with either the above-mentioned monomerscontaining vinyl or allyl functional groups with latent hydrolyzablegroups or with monomers containing vinyl or allyl groups without latenthydrolyzable groups to form the hyperbranched polymers of this inventionhaving at least two different types of functional groups includinghydrolyzable functional groups that are substantially uniformlydistributed throughout the hyperbranched polymer molecule and vinyl,allyl or hydrosilyl functional groups substantially uniformlydistributed as terminal end-groups of the hyperbranched polymermolecule.

[0020] Examples of monomers having vinyl or allyl reactive functionalgroups without latent hydrolyzable groups include diallyldimethylsilane,diallyldiphenylsilane, 1,3-diallyltetrakis-(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyl-disiloxane, 1,4-divinyltetramethyl-disilylethane,divinyltetraphenyldisiloxane, tris(vinyl-dimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.

[0021] The degree of branching of the hyperbranched polymers used inthis invention is not critical. However, the degree of branching issufficiently low (e.g., less than 95%, even less than 90%) todistinguish the hyperbranched polymers from dendrimers, which in theideal case have a degree of branching of 100%. The hyperbranchedpolymers used in this invention will typically have a degree ofbranching of from about 20% to about 55%, and more typically from about25% to about 45%. Such hyperbranched polymers can be easily prepared andare relatively inexpensive as compared with dendrimers.

[0022] The average degree of branching ({overscore (DB)}) is defined asthe number average fraction of branching groups per molecule, i.e., theratio of terminal groups plus branched groups to the total number ofterminal groups, branched groups, and linear groups. For ideal dendronsand dendrimers the degree of branching is 1. For ideal linear polymersthe degree of branching is 0. The degree of branching is expressedmathematically as follows:$\overset{\_}{DB} = \frac{N_{t} + N_{b}}{N_{t} + N_{b} + N_{l}}$

[0023] where N_(t) represents the number of terminal units, N_(b)represents the number of branched units, and N_(l) represents the numberof linear units, as defined in Hawker, C. J.; Lee, R. Fréchet, J. M. J.,J. Am. Chem Soc., 1991, 113, 4583.

[0024] The hyperbranched polymers used in this invention may generallyhave a weight average molecular weight of from about 1000 to about25,000; preferably from about 2000 to about 20,000; and more preferablyfrom about 2000 to about 10,000.

[0025] The hyperbranched polymers of this invention may be used forpreparing curable polymer compositions and cured compositions whereinthe hyperbranched polymers containing latent functional groups(functional groups that do not react significantly during polymerizationreaction but can react under a different set of conditions) arecovalently bonded to each other by reaction of the terminal end-groups(e.g., vinyl, allyl or hydrosilyl) with a connector or cross-linkingagent. In general, the hyperbranched polymers of this invention may becovalently connected to each other to form a nano-domain-structurednetwork using alpha,omega-telechelic linear polymers or oligomers,multi-functional linear polymers with functional groups pendant to themain chain backbone, and/or multi-functional randomly branched polymershaving functional groups regularly or randomly distributed in the mainor in the side chains. Other types of connectors may include di- ormulti-functional low molecular weight non-polymeric compounds that canreact with the terminal functional groups of the hyperbranched polymer.Connectors may also include multi-arm star polymers, dendrimers,dendrons, Combburst™ dendrigrafts, traditional branched polymers,homologously derivatized or other hyperbranched polymers, or otherarchitecturally specific macromolecules. Nano-domained networks formedfrom the hyperbranched polymers of this invention may be viewed asthree-dimensional, cross-linked materials comprising covalently bondednanoscopic, hyperbranched domains which may be of the same or differentchemical composition from the rest of the network, and which containlatent functional groups substantially uniformly distributed throughoutthe volume of the hyperbranched domains. Examples ofalpha,omega-telechelic linear polymers that may be used for connecting(i.e., cross-linking) include those having purely organic, or inorganic(such as siloxane), or organo-inorganic (such as carbosilane), backbone,with specific examples including polysiloxanes, such aspolydimethylsiloxane, and having appropriate terminal functional groupsthat will react with the terminal functional groups of the hyperbranchedpolymer molecules.

[0026] In accordance with a preferred aspect of this invention, curablecompositions can be prepared by combining the hyperbranched polymerswith the connectors or cross-linkers. Depending on the selection of thehyperbranched polymer or hyperbranched polymers and connectors orcross-linkers, and other additives, various coating compositions,adhesives, sealents, films, sheets, membranes or other objects may beprepared. Such compositions may be prepared as one-part systems well inadvance of their use, or as two-part systems that are combined justprior to use.

[0027] Depending on the chemistry utilized, initiators and catalysts maybe included in the composition in effective amounts as appropriate.Depending on the type of composition that is being produced, fillers,pigments, dies, antioxidants, fiber or particulate reinforcing agents,impact modifying agents, UV stabilizers, and the like may be added ineffective amounts. In certain applications, it may be desirable to addsmall amounts of solvents.

[0028] The curable compositions of this invention may contain onehyperbranched polymer or a combination of two or more differenthyperbranched polymers having the same or different chemical structureand having the same or different terminal groups. Similarly, the curablecompositions may contain a single connector or cross-linking agent, or acombination of two or more connectors/cross-linking agents.

[0029] The cured (cross-linked) nano-domain-structured networks may ormay not comprise domains of different chemical composition. However,architectural differences may result in different relative densities,shapes and sizes. Some of these structural features can be controlled byappropriate selection of precursor moieties and by the reactionconditions employed. In general, the relative size of hyperbranchedpolymers are smaller (ranging from about 1 to about 5, 10, or 15 nm)than their linear counterparts of equivalent molecular weight. Theresulting three-dimensional cross-linked materials comprise covalentlybonded nanoscopic, hyperbranched domains which may be of the same ordifferent chemical compositions than the linear polymers comprising therest of the network. These materials may be formed into films, sheets,membranes, coatings or other objects, and may exhibit glass transitiontemperatures that may rank them among either elastomers or plastomers.These and other properties of these networks depend on the selection ofprecursor polymers, including their chemical composition, moleculararchitecture, molecular weight and molecular weight distribution. Thematerials may also exhibit high thermal stability, mechanical strengthand toughness, and offer new ways for preparing specialty membranes,protective coatings, photoresists, novel composites, controlled porositymaterials, etc.

[0030] A particularly interesting use for the hyperbranched polymers ofthis invention (especially polycarbosilanes, polycarbosiloxanes,polycarbosilazenes and copolymers thereof) is in the preparation ofgaskets, o-rings, sealents, and sealing coatings exhibiting elasticity,heat resistance, and other properties comparable to conventionalsilicone compositions, but exhibiting improved mechanical properties(e.g., tensile strength and abrasion resistance) that are superior toconventional silicone compositions. In accordance with this aspect ofthe invention, latent hydrolyzable groups (e.g., ethoxy) substantiallyuniformly distributed throughout the volume of the hyperbranched domainsmay be reacted, such as with water, to undergo hydrolysis andcondensation to form nanoscopic silica-like inorganic structuredistributed throughout the hyperbranched domains. To increase thecross-link density of these structures, co-reactants, such astetraethoxysilane (TEOS), may be added into the domains containinglatent hydrolyzable groups either before or after the A+B polymerizationreaction. These nano-scaled silica-like, particle-like structures serveas in situ formed reinforcing agents that improve the mechanicalproperties of the composition. It is generally known that theimprovement in mechanical properties achieved with inorganic particulatereinforcing agents is inversely related to the average diameter of thereinforcing particles. In the scope of this invention, the inorganicparticle-like reinforcing structures have dimensions on the order offrom about 1 to about 5, 10, or 15 nm. Additionally, the inorganicsilica reinforcing structures of this invention are very uniformlydistributed throughout the hyperbranched domains and are covalentlybonded thereto, and therefore significantly improve the mechanicalproperties of the cured compositions of this invention. An illustrationof this procedure is shown in FIG. 1.

EXAMPLES Example 1

[0031] Preparation of Dual Functionalized Hyperbranchedpoly(carbosiloxane) HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H with Reactiveethoxysilyl and hydrosilane Groups from (CH₂═CHSi (OEt)₂)₂O andSi(OSiMe₂H)₄ (an A₂B₄+C₄ System)

[0032] A 250 ml two-necked, round-bottomed flask equipped with avertical cooling condenser was charged with 0.1550 gPlatinum-divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene). The flask was flushed with N₂ for 1min. A mixture of 1,3-divinyltetraethoxyldisiloxane (30.00 g, 95%, 92.98mmol) and tetrakis(dimethylsiloxy)silane (45.83 g, 139.40 mmol) waspoured into the two-necked, round-bottomed flask with stirring. Theresulting mixture was stirred at room temperature for 40 min., and thenheated in an oil bath kept at 50° C. for 16 h. The obtained viscous oilwas washed by acetonitril (50×3 ml). The volatiles were stripped off byrotvap in vacuum, and they were further dried in vacuo for 16 h to givea slightly yellowish oil (63 g). ¹H NMR in CDCl₃: 0.051 ppm (s, SiCH₃),0.056 ppm (s, SiCH₃), 0.065 ppm (s, SiCH₃), 0.112 ppm (s, SiCH₃), 0.119ppm (s, SiCH₃), 0.158 ppm (s, SiCH₃), 0.168 ppm (s, SiCH₃), 0.178 ppm(s, SiCH₃), 0.53-0.57 ppm (broad, m, CH₂CH₂), 1.09 ppm (d, CH ₃CH, J7.324 Hz, trace amount), 1.18 ppm (t, OCH₂ CH ₃, J 6.592 Hz), 3.78 ppm(q, OCH ₂CH₃, J 6.837 Hz), 4.68 ppm (m, SiH). ¹³C{¹H} NMR in CDCl₃:−1.13 ppm (s, SiCH₃), 0.13 ppm (s, SiCH₃), 2.75 ppm (s, SiCH₃), 6.54 ppm(s, CH₂CH₂), 7.39 ppm (s, CH₂CH₂), 8.79 ppm (s, CH₂CH₂), 18.05 (s, OCH₂CH₃), 57.96 ppm (s, OCH₂CH₃). ²⁹Si{¹H} NMR in CDCl₃: (−150.6)-(−104.0)ppm [m, Si(O—)₄], (−54.4)-(−52.7) ppm [m, Si(OEt)₂], (−6.6)-(−5.5) ppm(m, SiH), 8.9-10.1 ppm [m, Si(CH₃)₂]. IR on KBr disc (selectedresonance): 2133 cm⁻¹ [ν(SiH)], 960 cm⁻¹ [ν(Si—O—C₂H₅)]. GPC (Columnset: polymer lab columns 300×7.5 Plgel 10u mixed 10 M-MIXED −34−23, 10M-M34-2, Plgel 100 A, Plgel 50 A. Solvent: toluene. Standard:polystyrene 800-300,000): Mn 2809, Mw 7540, Polydispersity 2.68.

Example 2

[0033] Curing of HB-DVSi₂ (OEt)₄ DS-TDMSS-SiMe₂H of Example 1 withAlpha,Omega-Telechelic Vinyl-Terminated Polydimethylisloxane

[0034] CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂(MW 62,700, 1.20 g) wasdissolved in 3.5 mL hexanes in a 15 mL vial. To the solution were addedand dissolved in following sequence: 0.1 mL hexanes solution of3-methyl-1-pentyn-3-ol (0.30 g/mL); 0.1 mL hexanes solution ofplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene) (0.2 g xylene solution in 1 mLhexanes); HB-DVSi₂(OEt)₄ DS-TDMSS-SiMe₂H (0.30 g); and 0.1 g titaniumdi-n-butoxide(bis-2,4-pentanedionate) (73% in butanol). The resultingsolution was cast onto a Ti coated PET plate which was wet by (EtO)₄ Siand dried in the air prior casting, and the coating was cured at 120° C.for 20 min to yield an insoluble slightly yellowish coating.

Example 3

[0035] Curing of HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H Example of 1 With TwoAlpha,Omega-Telechelic Vinyl-Terminated Polydimethylsiloxanes (MW 62,700and MW 165,000)

[0036] CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 62,700, 0.9 g) andCH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 165,000, 0.9 g) were dissolvedin 8 mL hexanes in a 20 mL vial. To the solution were added anddissolved in the following sequence: 0.15 mL hexanes solution of3-methyl-1-pentyn-3-ol (0.20 g/mL); 0.15 mL hexanes solution ofplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene) (0.20 g xylene solution in 1 mLhexanes); HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H (0.45 g); 0.05 g titaniumdi-n-butoxide(bis-2,4-pentanedionate) solution (73% in butanol), and 0.2mL THF solution of (3-glycidoxypropyl)dimethylethoxysilane (0.25 g/ml).The resulting solution was cast onto a Ti coated PET plate, and cured at150° C. for 20 min to yield an insoluble slightly yellowish coating.

Example 4

[0037] Curing of HB-DVSi₂(OEt)₄DS-TDMSS-SiMe2H Example of 1 with Twoalpha,omega-telechelic vinyl-terminated polydimethylsiloxanes (MW 62,700and MW 165,000) and Post-Treatment with tetraethyl orthosilicate

[0038] CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 62,700, 8 g) andCH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 165,000, 8 g) were dissolved in20 mL hexanes in a 250 mL beaker. To the solution were added anddissolved in following sequence: 1.2 g 3-methyl-1-pentyn-3-ol; 0.20 gplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene); 4.0 g HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H;and 1.2 g titanium di-n-butoxide(bis-2,4-pentanedionate) solution (73%in butanol). Most volatiles were removed by blowing N₂ at the surface ofthe formulation. The resulting viscous solution was cast onto a mold anddried in the air for 4 days. It was then cured at 55° C. for 1 hour, 80°C. for 1.5 h, 155° C. for 1 hour to give a yellow brownish rubber, freeof air bubbles. Shore A durometer showed average reading 31.4. Theobtained silicone rubber was soaked in tetraethyl orthosilicate for 16hours, and kept at 150° C. in an oven for 1 hour to give a tougherelastic rubber. Shore A durometer showed average reading 40.

[0039] The above description is considered that of the preferredembodiments only. Modifications of the invention will occur to thoseskilled in the art and to those who make or use the invention.Therefore, it is understood that the embodiments described above aremerely for illustrative purposes and are not intended to limit the scopeof the invention, which is defined by the following claims asinterpreted according to the principles of patent law, including thedoctrine of equivalents.

The invention claimed is:
 1. A cross-linked polymer network, comprising:hyperbranched polymer domains having a plurality of each of at least onetype of potentially reactive functional groups; and a cross-linkercovalently bonding the hyperbranched polymer domains together.
 2. Thenetwork of claim 1, wherein at least one of the different types ofpotentially reactive functional groups is substantially uniformlydistributed throughout the hyperbranched polymer domains.
 3. The networkof claim 1, wherein at least one of the different types of potentiallyreactive functional groups is a hydrolyzable group substantiallyuniformly distributed throughout the hyperbranched polymer domains. 4.The network of claim 1, wherein at least one of the different types ofpotentially reactive functional groups is a hydrolyzable group bonded toa silicon atom substantially uniformly distributed throughout thehyperbranched polymer domains.
 5. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and at least one of the monomershaving at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer. 6.The network of claim 1, wherein the hyperbranched polymer is a productof a polymerization reaction of a first monomer having two or more vinylor allyl reactive functional groups (A) and a second monomer having twoor more hydrosilyl reactive functional groups (B), at least one of themonomers having three or more reactive functional groups and at leastone of the monomers having at least one latent functional group (C) thatdoes not react significantly during the polymerization of thehyperbranched polymer.
 7. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one reactive functional group of the first type(A), at least two reactive functional groups of the second type (B) andat least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer. 8.The network of claim 1, wherein the hyperbranched polymer is a productof a polymerization reaction of a monomer having at least one hydrosilylreactive functional group (A), at least two vinyl or allyl reactivefunctional groups (B) and at least one latent functional group (C) thatdoes not react significantly during the polymerization of thehyperbranched polymer.
 9. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one vinyl or allyl reactive functional group(A), at least two hydrosilyl reactive functional groups (B) and at leastone latent functional group (C) that does not react significantly duringthe polymerization of the hyperbranched polymer.
 10. The network ofclaim 1, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers has three or more reactive functional groups of the second type(B), at least one of the monomers having at least one latent functionalgroup (C) that does not react significantly during the polymerization ofthe hyperbranched polymer.
 11. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and wherein one of the monomershaving at least one latent functional group (C) and the other monomerhaving at least one latent functional group (D) wherein these latentfunctional groups may undergo reaction between themselves under thereaction conditions that are different from the polymerization reactionconditions.
 12. The network of claim 1, wherein the hyperbranchedpolymer is a product of a polymerization reaction of a monomer having atleast one reactive functional group of the first type (A), at least tworeactive functional groups of the second type (B) and at least twolatent functional groups (C and D) that do not react significantlyduring the polymerization of the hyperbranched polymer but may undergoreaction between themselves under the reaction conditions that aredifferent from the polymerization reaction conditions.
 13. The networkof claim 1, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers having three or more reactive functional groups of the secondtype (B), at least one of the monomers having at least two latentfunctional group (C and D) or at least one of the reacting monomershaving one type of latent functional groups (C) while at least one ofthe other monomers having at least one of another reactive functionalgroups (D) wherein the latent functional groups (C and D) do not reactsignificantly during the polymerization of the hyperbranched polymer butmay undergo reaction between themselves under the reaction conditionsthat are different from the polymerization reaction conditions.
 14. Thenetwork of claim 1, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having two or more hydrosilylgroups, and a monomer selected from the group consisting ofdiallyldimethylsilane, diallyldiphenylsilane,1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldisilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.
 15. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least two vinyl or allyl groups, and a monomerselected from the group consisting of 1,1,3,3-tetramethyldisiloxane,methyltris(dimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane,methylhydrocyclosiloxanes, tetrakis(dimethylsiloxy)silane,dimethylsilane, diethylsilane, diphenylsilane, phenylmethylsilane,methylsilane, and phenylsilane.
 16. The network of 1, wherein theconnector is an alpha,omega-telechelic linear polymer.
 17. The networkof claim 16, wherein the alpha,omega-telechelic linear polymer oroligomer has a polysiloxane backbone.
 18. The network of claim 16,wherein the alpha,omega-telechelic linear polymer or oligomer is apolydialkylsiloxane.
 19. The network of claim 1, wherein the connectoris a multi-functional linear polymer with functional groups pendant tothe main chain backbone.
 20. The network of claim 1, wherein theconnector is a multi-functional traditional branched polymer havingfunctional groups regularly or randomly distributed in the main or inthe side chains.
 21. The network of claim 1, wherein the connector is adi- or multi-functional non-polymeric compound that can react with theterminal functional groups at the surface of the hyperbranched polymer.22. The network of claim 1, wherein the connector is selected from thegroup consisting of multi-arm star polymers, dendrimers, dendrons,Combburst™ dendrigrafts and hyperbranched polymers.
 23. The network ofclaim 1, wherein crosslinking of the hyperbranched polymer precursor(s)was achieved by the hydrolysis of functional groups that weresubstantially uniformly distributed at the terminals of thehyperbranched polymer molecules.
 24. A cross-linked polymer networkcontaining nanoscopic reinforcing domains, comprising: a hyperbranchedpolymer domains containing reinforcing structures distributed in andcovalently bonded to the hyperbranched polymer; and a cross-linkercovalently bonding the hyperbranched polymer domains together.
 25. Thenetwork of claim 24, wherein the hyperbranched polymer is a product of apolymerization reaction of a first monomer having two or more reactivefunctional groups of the first type (A) and a second monomer having twoor more reactive functional groups of the second type (B), at least oneof the monomers having three or more reactive functional groups and atleast one of the monomers having at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 26. The network of claim 24, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more vinyl or allyl reactive functionalgroups (A) and a second monomer having two or more hydrosilyl reactivefunctional groups (B), at least one of the monomers having three or morereactive functional groups and at least one of the monomers having atleast one latent functional group (C) that does not react significantlyduring the polymerization of the hyperbranched polymer.
 27. The networkof claim 24, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having at least one reactivefunctional group of the first type (A), at least two reactive functionalgroups of the second type (B) and at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 28. The network of claim 24, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one hydrosilyl reactive functional group (A), atleast two vinyl or allyl reactive functional groups (B) and at least onelatent functional group (C) that does not react significantly during thepolymerization of the hyperbranched polymer.
 29. The network of claim24, wherein the hyperbranched polymer is a product of a polymerizationreaction of a monomer having at least one vinyl or allyl reactivefunctional group (A), at least two hydrosilyl reactive functional groups(B) and at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.30. The network of claim 24, wherein the hyperbranched polymer is aproduct of a polymerization reaction involving more than two mutuallyreactive monomers wherein at least one of the monomers has two or morereactive functional groups of the first type (A) and at least one of theother monomers has three or more reactive functional groups of thesecond type (B), at least one of the monomers having at least one latentfunctional group (C) that does not react significantly during thepolymerization of the hyperbranched polymer.
 31. The network of claim24, wherein the hyperbranched polymer is a product of a polymerizationreaction of a first monomer having two or more reactive functionalgroups of the first type (A) and a second monomer having two or morereactive functional groups of the second type (B), at least one of themonomers having three or more reactive functional groups and wherein oneof the monomers having at least one latent functional group (C) and theother monomer having at least one latent functional group (D) whereinthese latent functional groups may undergo reaction between themselvesunder the reaction conditions that are different from the polymerizationreaction conditions.
 32. The network of claim 24, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one reactive functional group of the first type(A), at least two reactive functional groups of the second type (B) andat least two latent functional groups (C and D) that do not reactsignificantly during the polymerization of the hyperbranched polymer butmay undergo reaction between themselves under the reaction conditionsthat are different from the polymerization reaction conditions.
 33. Thenetwork of claim 24, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers having three or more reactive functional groups of the secondtype (B), at least one of the monomers having at least two latentfunctional group (C and D) or at least one of the reacting monomershaving one type of latent functional groups (C) while at least one ofthe other monomers having at least one of another reactive functionalgroups (D) wherein the latent functional groups (C and D) do not reactsignificantly during the polymerization of the hyperbranched polymer butmay undergo reaction between themselves under the reaction conditionsthat are different from the polymerization reaction conditions.
 34. Thenetwork of claim 24, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having two or more hydrosilylgroups, and a monomer selected from the group consisting ofdiallyldimethylsilane, diallyldiphenylsilane,1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldislylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl- 1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, and divinyldimethylsilane.
 35. Thenetwork of claim 24, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having at least two vinyl or allylgroups, and a monomer selected from the group consisting of1,1,3,3-tetramethyldisiloxane, methyltris(dimethylsiloxy)silane,phenyltris(dimethylsiloxy)silane, methylhydrocyclosiloxanes,tetrakis(dimethylsiloxy)silane, dimethylsilane, diethylsilane,diphenylsilane, phenylmethylsilane, methylsilane, and phenylsilane. 36.The network of claim 24, wherein the connector is analpha,omega-telechelic linear polymer.
 37. The network of claim 36,wherein the alpha,omega-telechelic linear polymer or oligomer has apolysiloxane backbone.
 38. The network of claim 36, wherein thealpha,omega-telechelic linear polymer or oligomer is apolydialkylsiloxane.
 39. The network of claim 24, wherein the connectoris a multi-functional linear polymer with functional groups pendant tothe main chain backbone.
 40. The network of claim 24, wherein theconnector is a multi-functional traditional branched polymer havingfunctional groups regularly or randomly distributed in the main or inthe side chains.
 41. The network of claim 24, wherein the connector is adi- or multi-functional non-polymeric compound that can react with theterminal functional groups at the surface of the hyperbranched polymer.42. The network of claim 24, wherein the connector is selected from thegroup consisting of multi-arm star polymers, dendrimers, dendrons,Combburst™ dendrigrafts and hyperbranched polymers.
 43. The network ofclaim 24, wherein the inorganic structures distributed in and covalentlybonded to the hyperbranched polymer are the in situ condensation productof hydrolyzable groups bonded to a silicon atom.
 44. The network ofclaim 24, wherein the inorganic structures distributed in and covalentlybonded to the hyperbranched polymer have dimensions of from about 1 toabout 15 nanometers.
 45. A process for making a cross-linked polymernetwork, comprising the step of: reacting a hyperbranched polymer havinga plurality of each of at least two different types of functional groupswith a cross-linker that covalently bonds the hyperbranched polymermolecules together.
 46. The process of claim 45, wherein at least one ofthe different types of functional groups is substantially uniformlydistributed throughout the hyperbranched polymer molecule and at leastone other of the two different functional groups is substantiallyuniformly distributed at the terminals of the hyperbranched polymermolecule.
 47. The process of claim 45, wherein at least one of thedifferent types of functional groups is a hydrolyzable group bonded to asilicon atom substantially uniformly distributed throughout thehyperbranched polymer molecule and the other of the different functionalgroups is substantially uniformly distributed at the terminals of thehyperbranched polymer molecule.
 48. The process of claim 45, wherein atleast one of the different types of functional groups is a hydrolyzablegroup substantially uniformly distributed throughout the hyperbranchedpolymer molecule and the other of the different functional groups is ahydrosilyl, vinyl or allyl group.
 49. The process of claim 45, whereinthe hyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and at least one of the monomershaving at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.50. The process of claim 45, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a first monomer having two ormore vinyl or allyl reactive functional groups (A) and a second monomerhaving two or more hydrosilyl reactive functional groups (B), at leastone of the monomers having three or more reactive functional groups andat least one of the monomers having at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 51. The process of claim 45, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one reactive functional group of the first type(A), at least two reactive functional groups of the second type (B) andat least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.52. The process of claim 45, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a monomer having at least onehydrosilyl reactive functional group (A), at least two vinyl or allylreactive functional groups (B) and at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 53. The process of claim 45, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one vinyl or allyl reactive functional group(A), at least two hydrosilyl reactive functional groups (B) and at leastone latent functional group (C) that does not react significantly duringthe polymerization of the hyperbranched polymer.
 54. The process ofclaim 45, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers has three or more reactive functional groups of the second type(B), at least one of the monomers having at least one latent functionalgroup (C) that does not react significantly during the polymerization ofthe hyperbranched polymer.
 55. The process of claim 45, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and wherein one of the monomershaving at least one latent functional group (C) and the other monomerhaving at least one latent functional group (D) wherein these latentfunctional groups may undergo reaction between themselves under thereaction conditions that are different from the polymerization reactionconditions.
 56. The process of claim 45, wherein the hyperbranchedpolymer is a product of a polymerization reaction of a monomer having atleast one reactive functional group of the first type (A), at least tworeactive functional groups of the second type (B) and at least twolatent functional groups (C and D) that do not react significantlyduring the polymerization of the hyperbranched polymer but may undergoreaction between themselves under the reaction conditions that aredifferent from the polymerization reaction conditions.
 57. The processof claim 45, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers having three or more reactive functional groups of the secondtype (B), at least one of the monomers having at least two latentfunctional group (C and D) or at least one of the reacting monomershaving one type of latent functional groups (C) while at least one ofthe other monomers having at least one of another reactive functionalgroups (D) wherein the latent functional groups (C and D) do not reactsignificantly during the polymerization of the hyperbranched polymer butmay undergo reaction between themselves under the reaction conditionsthat are different from the polymerization reaction conditions.
 58. Theprocess of claim 45, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having two or more hydrosilylgroups, and a monomer selected from the group consisting ofdiallyldimethylsilane, diallyldiphenylsilane,1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldisilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.
 59. The process of claim 45, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least two vinyl or allyl groups, and a monomerselected from the group consisting of 1,1,3,3-tetramethyldisiloxane,methyltris(dimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane,methylhydrocyclosiloxanes, tetrakis(dimethylsiloxy)silane,dimethylsilane, diethylsilane, diphenylsilane, phenylmethylsilane,methylsilane, and phenylsilane.
 60. The process of claim 45, wherein theconnector is an alpha,omega-telechelic linear polymer.
 61. The processof claim 45, wherein the alpha,omega-telechelic linear polymer oroligomer has a polysiloxane backbone.
 62. The process of claim 45,wherein the alpha,omega-telechelic linear polymer or oligomer is apolydialkylsiloxane.
 63. The process of claim 45, wherein the connectoris a multi-functional linear polymer with functional groups pendant tothe main chain backbone.
 64. The process of claim 45, wherein theconnector is a multi-functional traditional branched polymer havingfunctional groups regularly or randomly distributed in the main or inthe side chains.
 65. The process of claim 45, wherein the connector is adi- or multi-functional non-polymeric compound that can react with theterminal functional groups at the surface of the hyperbranched polymer.66. The process of claim 45, wherein the connector is selected from thegroup consisting of multi-arm star polymers, dendrimers, dendrons,Combburst™ dendrigrafts and hyperbranched polymers.
 67. The process ofclaim 45, wherein the crosslinking of the hyperbranched polymerprecursor(s) is achieved by the hydrolysis of functional groups thatwere substantially uniformly distributed at the terminals of thehyperbranched polymer molecules.
 68. A process for making a cross-linkedpolymer network containing nanoscopic reinforcing domains comprising thestep of: reacting a hyperbranched polymer containing reinforcingstructures distributed in and covalently bonded to the hyperbranchedpolymer with a cross-linker to covalently bond the hyperbranched polymermolecules together.
 69. The process of claim 68, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and at least one of the monomershaving at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.70. The process of claim 68, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a first monomer having two ormore vinyl or allyl reactive functional groups (A) and a second monomerhaving two or more hydrosilyl reactive functional groups (B), at leastone of the monomers having three or more reactive functional groups andat least one of the monomers having at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 71. The process of claim 68, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one reactive functional group of the first type(A), at least two reactive functional groups of the second type (B) andat least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.72. The process of claim 68, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a monomer having at least onehydrosilyl reactive functional group (A), at least two vinyl or allylreactive functional groups (B) and at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 73. The process of claim 68, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one vinyl or allyl reactive functional group(A), at least two hydrosilyl reactive functional groups (B) and at leastone latent functional group (C) that does not react significantly duringthe polymerization of the hyperbranched polymer.
 74. The process ofclaim 68, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers has three or more reactive functional groups of the second type(B), at least one of the monomers having at least one latent functionalgroup (C) that does not react significantly during the polymerization ofthe hyperbranched polymer.
 75. The process of claim 68, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and wherein one of the monomershaving at least one latent functional group (C) and the other monomerhaving at least one latent functional group (D) wherein these latentfunctional groups may undergo reaction between themselves under thereaction conditions that are different from the polymerization reactionconditions.
 76. The process of claim 68, wherein the hyperbranchedpolymer is a product of a polymerization reaction of a monomer having atleast one reactive functional group of the first type (A), at least tworeactive functional groups of the second type (B) and at least twolatent functional groups (C and D) that do not react significantlyduring the polymerization of the hyperbranched polymer but may undergoreaction between themselves under the reaction conditions that aredifferent from the polymerization reaction conditions.
 77. The processof claim 68, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers having three or more reactive functional groups of the secondtype (B), at least one of the monomers having at least two latentfunctional group (C and D) or at least one of the reacting monomershaving one type of latent functional groups (C) while at least one ofthe other monomers having at least one of another reactive functionalgroups (D) wherein the latent functional groups (C and D) do not reactsignificantly during the polymerization of the hyperbranched polymer butmay undergo reaction between themselves under the reaction conditionsthat are different from the polymerization reaction conditions.
 78. Theprocess of claim 68, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having two or more hydrosilylgroups, and a monomer selected from the group consisting ofdiallyldimethylsilane, diallyldiphenylsilane,1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldisilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.
 79. The process of claim 68, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least two vinyl or allyl groups, and a monomerselected from the group consisting of 1,1,3,3-tetramethyldisiloxane,methyltris(dimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane,methylhydrocyclosiloxanes, tetrakis(dimethylsiloxy)silane,dimethylsilane, diethylsilane, diphenylsilane, phenylmethylsilane,methylsilane, and phenylsilane.
 80. The process of claim 68, wherein theconnector is an alpha,omega-telechelic linear polymer.
 81. The processof claim 68, wherein the alpha,omega-telechelic linear polymer oroligomer has a polysiloxane backbone.
 82. The process of claim 68,wherein the alpha,omega-telechelic linear polymer or oligomer is apolydialkylsiloxane.
 83. The process of claim 68, wherein the connectoris a multi-functional linear polymer with functional groups pendant tothe main chain backbone.
 84. The process of claim 68, wherein theconnector is a multi-functional traditional branched polymer havingfunctional groups regularly or randomly distributed in the main or inthe side chains.
 85. The process of claim 68, wherein the connector is adi- or multi-functional non-polymeric compound that can react with theterminal functional groups at the surface of the hyperbranched polymer.86. The process of claim 68, wherein the connector is selected from thegroup consisting of multi-arm star polymers, dendrimers, dendrons,Combburst™ dendrigrafts and hyperbranched polymers.
 87. The process ofclaim 68, wherein the crosslinking of the hyperbranched polymerprecursor(s) is achieved by the hydrolysis of functional groups thatwere substantially uniformly distributed at the terminals of thehyperbranched polymer molecules.
 88. The process of claim 68, whereinthe inorganic structures distributed in and covalently bonded to thehyperbranched polymer are the in situ condensation product ofhydrolyzable groups bonded to a silicon atom.
 89. The process of claim68, wherein the inorganic structures distributed in and covalentlybonded to the hyperbranched polymer have dimensions of from about 1 toabout 15 nanometers.